Photographic multilayer material for color photographic purposes



Oct. 29, 1940. l B. GAsPA u 2,219,305

Pnroennmc summum MATERIAL Fon coLoR PaoToenArnrc PunPosEs Filed Deo. s,19:59

auf www1/Paw MGM/W arm (Titou-neg Patented Oct. 29, 1940 i UNITED STATESPATENT vori-*lcs PHOTOGRAPHIC MULTILAYER MATERIAL FOR COLGR PHOTOGRAPHIOPURPOSES Bla Gspr, Hollywood, Calif.

Application December 3, 1938, Serial No. 243,889 In Great BritainDecember 9, 193'] 5 Claims.

i necessary for the formation of the final image.

As is known, such light-sensitive materials after yexposure of thelight-sensitive layers, are converted into lcolored pictures by means oflocal removal of the dyestuif. Iftwo or more layers are arranged uponthe same support, it is necessary to sensitise at least two of thelayers for diierently colored light in order to produce the desiredcolor selection picture in each individual layer with lightcorresponding to the sensitivity. A suitable sensitisation has beendescribed in my United States Patent Ofiice No. 1,985,344, dated Dec.25, 1934. In the case of a printing material with al transparent supportand withfcolored layers arranged on one or both sides thereof, as usedfor the production of color iilms or transparencies, the rst and therear layer can'be printed if desired from each side respectively. Inthis case these two layers may have the same sensitivityv while thecolored layer lying between acts optically as a screen. Thus, forexample, in my United States Patent 2,183,393, Dec. 12, 1939 describinga three-layer iilm, an intensively colored yellow emulsion layer liesbetween two blue-sensitive layers ofv which the one is, coloredpurple-red m and the other blue-green, the yellow dyestuff serving forthe composition of the image and acting a,s a filter during the printingoperation.

-Now it has been found that it is not possible in all cases to limit theexposure of a blue-sensitive B5 layer or, in the case above referred to,of vthe two blue-sensitive layers, to these layers. Sometimes theyellow-colored silver halide layer behind the blue-sensitive layer or*the middle layer in the above mentioned example is also influ- Io encedby the light used for the exposure of the 50 red by -a panchromaticsensitizer which imparts a outer layers. The same phenomenon appears notonly in the'example described of a yellow layer, but also can beobserved, if green light falls upon a purple-colored layer, containing asensitizer which renders lt sensitive for green light as, for example,the middle layer of the material shown in Figure 1 of my United StatesPatent No. 1,985,344, if this layer be rendered sensitive to sensitivityto green light in addition to the sensitivity tored light. Thisundesired exposure results .in a small defect of the prints, hardlyvisible during projection, but undesirable in viewof the 55 modernrequirements and disadvantageous in certain cases as, for example, inthe copying of such a picture.

It has been found that the yphenomenon described above can be suppressedby increasing the concentration of the dye to such an extent thatv thelayer is more effectively screened against the action of lightcomplementary to the color of the layer. The concentration required foreiectively shielding the layer is, howeveiylhigher than that requiredfor correct color reproduction. Thus, the problem is not only theincrease in dyestuff concentration but further the surplus of the dyemust be removed during the process -and preferably without an increaseof the treatment time.

'Ihe subjectof the present invention is a material having a suiiicientlyhigh concentrl'ation of dye for the color separation and allowing aquick processing of the material.

For this purpose the layers are dyed to a color intensity higher thanrequired by the most intensely colored parts 'of the nal image and,therefore, suiiiciently high for the color separation. Two dyestuifs ofvery different resistance against the treating solutions are used forthis purpose. The image is formed substantially by one of these dyesalone, the other dyestu lbeing ytotally removed from the image.-

Accordingly, the invention consists of a lightsensitive :multilayersilver halide material, in which at least one light-sensitive layer isformed by an emulsion which in its uncolored state would be sensitivenot only to. light for which the layer is predominantly sensitised andto which it is intended to be exposed but also to light for which a.superimposed light-sensitive layer is sensitive or f to be exposed.According to the invention the layer is dyed by a mixture of thedyestuff intended to form the nal image inthe layer and a seconddyestuii' of similar color. The dyestuff used for the formation of thedyestui image 'is fast to ordinary photographic treating solutions andcapable of being bleached out under the influence of the silver image.This dyestu' is used in a concentration which corresponds to the colorintensity necessary for a reproduction of .the :most .intensely coloredparts of the picture. The auxiliary dyestuff is of practically the samecolor but of much larger bleaching capacity than the dy'estuff for theformation of the image and can be totally removed by treating solutionsharmless .to the image forming dyestuff. The quantity of the auxiliarydyestuif is chosen in such a manner that its absorption in addition tothat of the image forming dyestuif is practically suiiicie'nt fOrpreventing any light of complementarycolor to enter the layer. Thisimage forming dycstu may be bleached locally preferably prior to butalso during or subsequent to the removal or destruction of the auxiliarydyestuff and the destruction has the effect of lowering the colorintensity to that required for a reproduction of the most intenselycolored parts of the picture.

Example 1 As shown in Fig. I of the drawing a silver halide emulsionlayer sensitised to green or red light and dyed by a mixture of thedyestuff Xylenewalkgelb (Sandoz, Handbuch der Faerberei, 1926, 2nd ed.)and the auxiliary dyestuff 4,4methenyl bis- [1-(p-sulphophenyl)-3-methyl-pyrazolone-5l is arranged between a blue-sensitive silverhalide emulsion dyed magenta by the N-methyl-naphtho-quinolinium salt ofthe dyestuff Tuchechtbrillantrot 2B, and a blue-sensitive silver halidelayer surface N-methyl-naphtho-quinolinium salt of the dyestuffTuchechtbrillantrot 2B 1.2

Triphenyl-guanidine salt of 4,4'methenyl bis- 1 p sulphophenyl)--methyl-pyrazolone-5]; 1 Calcium salt of Xylenewalkgelb G 1.4 PontamineSky Blue 5BX 0.6

The material may be used for the production of dyestuff images in themanner described in my aforementioned Patent 2,183,393. The dyestuff4.4methenylbis[1(p-sulphophenyl) -S-methylpyrazolone-5] and itspreparation is described in my application Ser. No. 240,860 led Nov. 16,1938. The dyestuff is decolorised by an alkaline developer or bysolutions containing sulphite or bisulphite compounds.

Example 2 In Fig. II I have shown that the support which in this casecan be opaque, carries a silver halide layer which is colored blue-greenwith the N- methyl-naphtho-quinolinium salt of the dyestuff Ponta'mineSky Blue 5BX and sensitised with cryptocyanine for infra-red light. Thislayerl contains further a destructible blue-green dyestui, viz., thedyestuff obtained from l-(p-sulphophenyl)3methylpyrazolone5 andglutaconic-dialdehyde-dianilide. Instead of being incorporated withinthe layer4 the dyestuff may be applied by the aid of a thin gelatinlayer containing the auxiliary dyestuil' in a concentration of 0.5 g.per sq. m. the gelatin being poured upon the rst layer. A silver halideemulsion layer, sensitised to red light by pinacyanole, and coloredmagenta with the N-methyl-naphtho-quinoy linium salt ofTuchechtbrillantrot 2B, is etiher coated directly on the blue-greenlayer or layers or on an intermediary layer of colorless gelatin.

VThe magenta layer, its surface or a separate layer lying above containsa red dyestuff which may be, for example, the diphenyl-guanidine salt ofthe sulphonnic acid derived from methenyl-bis-oxythionaphthene which maybev prepared by adding di-phenyl guanidine, dissolved ln water with 1511addition of acetic acid, to the dyestuff solution. A yellow coloredsilver halide emulsion as described in Example 1 is sensitised to greenand used in front of the other layers.

The quantity of dyestuff depends upon the use of the material. In thecase of an image on a transparent support for projection or fortransparencies, the dyestui concentrations may be the same as given inExample 1, whereas in a material for the production of colored images ona paper support the concentration of the imageforming dyestuii isdecreased toabout 1/2 or 1/3 of the amounts given in Example 1, whereasthe concentration of the auxiliary dyestuff is increasedcorrespondingly.

As already described in connection with Example 2 the auxiliary dyestuffhaving the same or similar color as the image-forming dyestuff may beincorporated in an additional or intermediate layer arranged in front ofthe light-sensitive layer colored with the image-forming dyestuff. Theauxiliary layer may also be light-sensitive and in this case should besensitised for a spectral range which allows a separate exposure of theintermediate layer as described in my copending application Ser. No.243,886, led Dec. 3, 1938. In this case the auxiliary dyestuff may bedestroyed, after diffuse illumination of the intermediate layer anddeveloping, by the dyestuff destroying agent which locally destroys thedyestuffs within the image-bearing layers, such as, for instance, 5%hydrobromic acid or an acid thiocarbamide solution.

What is claimed is:

1. Light-sensitive multilayer material comprising a plurality of silverhalide emulsion layers dyed with fast dyes necessary for the formationof a multicolor picture, at least one of which is formed by an emulsionwhich in its uncolored state would be sensitive not only to the lightfor which the layer is predominantly sensitized and to which it is to beexposed but also to a dierently colored light to be used for theexposure of another of said fast dyed light-sensitive layers situated infront thereof, said other layer being both predominantly sensitive toand at least partially transparent to such differently colored light,the fast dyestuff in the layer first referred to being a dyestuff whichabsorbs said differently colored light transmitted by the superposedlayer and being fast to ordinary photographic treating solutions andbeing capable of being bleached under the influence of the silver image,the dyestuff further being present in a concentration which is necessaryfor the, reproduction of the most intensely colored parts of thevpicture, a layer of the multilayer material behind said other layercontaining additional dyestuff of substantially the same color as thefirst-named dyestuff but removable by an agent which does' not removethe mst-named dyestuff, the amount of fast dyestun' and additionaldyestuff together being sumcient to prevent any light of complementarycolor from entering the said first referred to fast-dyed light-sensitivelayer.

2. Light-sensitive multilayer material comprising a plurality of silverhalide emulsion layers dyed with fast dyes necessary for the formationof a multicolor picture, at least one of which is formed by an emulsionwhich in its unoolored state would be sensitive not only to the lightfor which the layer is predominantly sensitized and to which it is to beexposed but also to a dierently colored light to be used for theexposure of another of said fast dyed light-sensitive layers situated infront thereof, said other layer being at least partially transparent tosuch differently colored light, the fast dyestuf in the layer rstreferred to being a dyestuif which absorbs light rays transmitted by thesuperposed layer and being fast to ordinary photographic .nameddyestuif, the amount of fast dyestuff and additional dyestufl togetherbeing suflicient to prevent any light of complementary color fromentering the said first referred to fast-dyed lightsensitive layer. I y3. Light-sensitive multilayer material comprising a plurality of silverhalide emulsion layers dyed with fast dyes necessary for the formationof, a multicolor picture, at least one of which is formed by an emulsionwhich in its uncolored state would be sensitive not only to the lightfor which the layer is predominantly sensitized and to which it is to beexposed but also to a differently colored light to be used for theexposure of another of sa'id fast dyed light-sen- A sitive layerssituated in front thereof, said other layer being at least partiallytransparent to such differently colored light, the fast dyestuli` in thelayer rst referred to being a dyestui which absorbs light raystransmitted by the superposed layer and being fast to ordinaryphotographic treating solutions and being capable of being bleachedunder the influence of the silver image, the dyestuff further beingpresent in av concentration which is necessary for the reproduction ofthe most intensely colored parts of the picture,'an intermediate layerbetween the layer first referred to and thesaid other layer situated infront thereof containing an additional dyestui of substantially the samecolor as the first-named dyestuff but removable byv an agent which doesnot remove the'flrst-named dyestuff, the amount of fast dyestuff andadditional dyestuff together being sufficient to prevent any light` ofcomplementary color from entering the said `first referred to fast-dyedlight-sensitive layer.

4. A light-sensitive multilayer material -comprising a plurality ofsilver halide emulsion layers, at least one of which is formed by a dyedemulsion which in its uncolored state would be sensitive not only to thelight for which th layer is predominantly sensitized and to which it isto be exposed but also to a differently colored light to be used for theexposure of another light-sensitive llayer situated in front thereof,said other layer being at least partially transparent to suchdifferently colored light, the layer flrst referred to being coloredwith a dyestuff which absorbs said differently colored light transmittedby said other layer, said dyestuf being fast to ordinary photographictreating solutions and being capable of being bleached under theinfluence of the silver image, said dyestuif further being present in aconcentration which 'is neces- Sary Afor the reproduction of the mostintensely colored parts of the picture, a layer of the multilayermaterial behind said other layer contain, ing an additional dyestuff ofsubstantially the same color as the first-named dyestuif but removableby an agent which does not remove said first-named dyestuff, the amountof fast dyestuif and additional dyestuff together being sufflcient toprevent any of said differently colored light from entering the said rstreferred to light-sensitive layer.

5. A lightsensitive multilayer material comprising a plurality of silverhalide emulsion layers, at least one of which is formed by a dyedemulsion which in its uncolored state would be sensitive not only to thelight for which the layer is predominantly sensitized and to which it isto be exposed but also to a differently colored light to be used for theexposure of another light` sensitive layer situated in front thereof,said other layer being atleast partially transparent to such differentlycolored light, the layer first referred to being colored with a dyestuffwhich absorbs said differently colored light transmitted by said otherlayer, said dyestui being fast to ordinary photographic treatingsolutions and being capable of being bleached under the influence of thesilver image, said dyestui further being present in a concentrationwhich is necessary for the reproduction of the most intensely coloredparts of the picture, the layer first referred to containing anadditional dyestuff of substantially the same color as the first-nameddyestuif but removable by an agentwhich does not remove the first-nameddyestuff, the amount of fastdyestuff and additional dyestuff togetherbeing sufficient to prevent any of s aid differently colored light fromentering the said flrst referred to light-sensitive layer.

BLA GASPAR.

